Peptide‐Modulated Self‐Assembly of Chromophores toward Biomimetic Light‐Harvesting Nanoarchitectonics

Abstract

Elegant self-assembling complexes by the combination of proteins/peptides with functional chromophores are decisively responsible for highly efficient light-harvesting and energy transfer in natural photosynthetic systems. Mimicking natural light-harvesting complexes through synthetic peptides is attractive due to their advantanges of programmable primary structure, tunable self-assembly architecture and easy availability in comparison to naturally occuring proteins. Here, an overview of recent progresses in the area of biomimetic light-harvesting nanoarchitectonics based on peptide-modulated self-assembly of chromophores is provided. Adjusting the organization of chromophores, either by creating peptide-chromophore conjugates or by the non-covalent assembly of peptides and chromophores are highlighted. The light-harvesting properties, especially the energy transfer of the biomimetic complexes are critically discussed. The applications of such complexes in the mineralization of inorganic nanoparticles, generation of molecular hydrogen and oxygen, and photosynthesis of bioactive molecules are also included.

Broad‐Spectrum Tunable Photoluminescent Nanomaterials Constructed from a Modular Light‐Harvesting Platform Based on Macrocyclic Amphiphiles

“…[3] Toward this goal, light-harvesting systems involving energy migration can be exploited for the generation of multiple fluorescent emissions by tuning the energy-transfer efficiency between donor-acceptor components. [3b,4] Inspired by nature, scientists have demonstrated a diverse array of artificial lightharvesting systems based on various scaffolds, including dendrimers, [5] micelles/ vesicles, [6] gels, [7] (bio)-polymer assemblies, [8] host-guest ensembles, [9] and organic-inorganic hybrid materials. [10] However, many current approaches require covalent integration of either the donor or the acceptor, or even both, not only limiting the synthetic accessibility but also hampering easy access to large libraries of light-harvesting entities and their high-throughput testing.…”

Amyloid scaffolds as alternative chlorosomes

“…The π-π interactions and electrostatics between the negatively charged porphyrin and positively charged dipeptides (KK) collectively drive solution phase assembly of these components into powerful light-harvesting antennae with the potential for hydrogen evolution. 55–57 The amyloid templates provide a well-defined peptide scaffold with the potential for self-propagation and evolutionary selection within a cellular matrix. To extend the chlorosome model, we needed to increase the architectural and functional capability of amyloid nanotube assemblies.…”

D-amino acid-containing supramolecular nanofibers for potential cancer therapeutics

“…To mimic those biological systems, researchers have utilized sugar derivatives [4-7], amino acid derivatives [8, 9], DNA [10, 11], lipids [12, 13], and peptides [6, 7, 14] as the building blocks to construct a wide-range of nanomaterials. Among these, self-assembling peptides have attracted increasing attentions in recent years due to their easiness in design and synthesis [15-19]. Moreover, their readily modifiable and known functional motifs, good biocompatibility, low immunogenicity, minimal toxicity, inherent biodegradability, and fast responses to external stimuli have resulted in the applications of self-assembling peptides in various biomedical applications, such as three dimensional cell culture [20-24], drug delivery [25-33], cancer therapy [34-37], immune boosting [38-41], regenerative medicine [20, 42-44], and detection of important analytes (e.g., enzymes, metal ions, bacteria) [4, 45-52].…”